Living cationic polymerization of alkyl vinyl ethers

ABSTRACT

This invention relates to a process for the living cationic polymerization of vinylic unsaturated compounds containing electron donating substituents resulting in polymers of narrow molecular weight distribution.

FIELD OF THE INVENTION

This invention relates to a process for the living cationic polymerization of vinylic unsaturated compounds containing electron donating substitutes to polymers of narrow molecular weight distribution.

BACKGROUND OF THE INVENTION

Living polymerization allows for the synthesis of new polymers and oligomers with specialized structures. A number of recent advances have occurred in polymerization by cationic mechanisms to yield living polymers, where it was previously thought that obtaining living characteristics was unlikely, except for a few ring-opening polymerization systems, due to the reactivity or instability of the ions involved.

T. Higashimura and M. Sawamoto; Adv. Polym. Sci., 1984, 62, 50-94, review the attempts at living cationic polymerization of vinyl monomers and state that until recently it was considered "beyond our reach." They teach away from using oxo acids, such as sulfonic acids, because they believe that the acid derived counterions react with the propagating cations and thereby terminate the polymerization. For example, they show in Table 11 that dimer instead of polymer is produced when p-methoxystyrene is reacted with either CH₃ SO₃ H or CF₃ SO₃ H. They disclose the use of an HI/I₂ initiating system to polymerize isobutyl vinyl ether in n-hexane. They claim this polymerization system to be the first example of living cationic polymerization of vinyl compounds.

M. Miyamoto, M. Sawamoto, and T. Higashimura; Macromol., 1984, 17, 265-268, show that living polymerization of isobutylvinyl ether using HI/I₂, I₂, or HI as initiators, does not occur in a polar solvent such as CH₂ Cl₂.

S. Aoshima and T. Higashimura; Polym. Bull., 1986, 15, 417-423, disclose the use of esters as Lewis base modifiers for EtAlCl₂. These systems are used as initiators for the living cationic polymerization of vinyl ethers.

T. Higashimura, Y. Kishimoto, and S. Aoshima, Polym. Bull., 1987, 18, 111-115, disclose the use of an EtAlCl₂ /dioxane (basic compound) initiating system for the living cationic polymerization of vinyl monomers. A small amount of water is added to the initiating system.

R. Faust and J. P. Kennedy; Polym. Bull., 1986, 15, 317-323, describe the living carbocationic polymerizations of isobutene using initiating complexes of organic esters with Lewis acids.

EP 206, 756, discloses the use of complexes of Lewis acids and organic acids or esters as catalysts for the living polymerization of olefins and diolefins.

JP J6 0228-509, discloses the preparation of polyalkenyl ethers by living polymerization using as catalysts iodine and optionally HI.

U. S. Pat. No. 4,393,199 discloses a method of polymerizing monomers capable of cationic polymerization by using an adduct consisting of a preinitiator precursor and a catalyst, to react with the monomer and produce a polymer of low polydispersity.

U. S. Pat. No. 4,696,988 discloses the use of HI/I₂ initiating systems to polymerize isopropenylphenyl glycidyl ethers. The use of CF₃ SO₃ H is shown to be ineffective.

It is difficult to predict which initiator/Lewis base combinations will result in a living cationic polymerization of a vinyl monomer. For example, S. Aoshima and T. Higashimura, op. cit., show that living polymerizations of 2-vinyloxyethyl benzoate and 2-vinyloxyethyl methacrylate monomers, where the ester functioning as a Lewis base is incorporated within its structure, can be conducted using EtAlCl₂ but not with BF₃ OEt₂.

The present invention provides a process for the cationic polymerization of vinylic unsaturated compounds using a proton or carbenium or siliconium ion source, and/or Lewis acids; in combination with selected Lewis base.

SUMMARY OF THE INVENTION

The present invention provides a process for the preparation of polymers by cationic polymerization of selected vinylic unsaturated compounds using a suitable initiator, examples of which include a combination of a proton source (HA) and a Lewis base (LB); HA, Lewis acid (LA) and LB; carbenium or siliconium ion source (CS) and LB or CS, LA and LB. Examples of HA include; CF₃ SO₃ H, H₂ SO₄, FSO₃ H, HClO₄, HCO₂ R (where R is C₁₋₄ alkyl), HOR, HSR, and H₂ O. Examples of LA include; BF₃, RAlCl₂, PF₅, AsF₅, and SbF₅. When the HA used is weakly acidic, e. g. HCO₂ R, HOR, HSR, or H₂ O, a Lewis acid is necessary for polymerization to occur. Examples of LB include; CH₃ SR¹, where R₁ is a straight chain C₁₋₄ alkyl, (CH₃ CH₂)₂ S, (CH₃ CH₂ CH₂)₂ S, CH₃ CH₂ SH, (CH₃)₂ SO, CH₃ SCH₂ SCH₃, CH₃ SCH₂ CH₂ SCH₃, tetrahydrofuran (THF), tetrahydrothiophene diisopropyl sulfide, or p-dioxane. Examples of carbenium and siliconium ion sources (CS) include; CF₃ SO₃ R, CF₃ SO₃ SiR₃, R² CH(OR)₂, R² C(OR)₃ and R² C(O)H, where R² is phenyl or C₁₋₆ alkyl and R is as defined above.

The polymerization reaction proceeds according to the following formula:

    nCH.sub.2 ═C(X)H+n.sup.I HA+n.sup.II LA+n.sup.III LB+n.sup.IV CS

where n.sup.(I-IV) denotes the proportions of the number of moles of reactants; n=1-200, n^(I) =0-1, n^(II) =0-10, n^(III) =1-50, and n^(IV) =0-1 with the proviso that n^(I) +n^(IV) =1; and X is an electron donating group such as a C₁₋₆ alkoxy group.

DETAILS OF THE INVENTION

The monomers useful in the invention process include, but are not limited to, styrenes with para alkyl or alkoxy substiuents, where the alkyl or alkoxy groups contain C₁ to C₆ carbon atoms; alkyl vinyl ethers or aralkyl vinyl ethers, where the alkyl groups contain one to twenty carbon atoms, and optionally contain halogen atoms such as chlorine, fluorine or bromine, or ether linkages; and N-vinylcarbazole. Preferably the monomer is a, C₁ to C₆ alkyl vinyl ether. Most preferred are methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether. The monomers used herein are either known compounds or can be prepared by known methods.

In the invention process, a monomer is polymerized in a suitable solvent, preferably dichloromethane or hexane, in an inert gas atmosphere, with precautions being taken to exclude water, except when water is deliberately added as part of the initiator system, at temperatures of about -80° C. to about 0° C. Pressure is not critical, but atmospheric pressure is preferred. Preferred HA's, LA's and CS's include; FSO₃ H, SbF₅, CF₃ SO₃ Si(CH₃)₃, BF₃, CF₃ SO₃ H, PhC(O)H, PhCH(OCH₃)₂. A Lewis base is a necessary component of the catalyst system in order to obtain a narrow molecular weight distribution (MWD) polymer, indicative of a living polymerization. It is believed that the polymer products of this invention are examples of living cationic polymerization, as evidenced by the dependence of M_(n) on [M]_(o) /[I]_(o) and the narrow MWD of the products. Because the polymers of this invention are living, they can be used to prepare block copolymers. Lewis bases used in the process of this invention are CH₃ SR¹ , where R¹ is a straight chain C₁₋₄ alkyl, (CH₃ CH₂)₂ S, (CH₃ CH₂ CH₂)₂ S, CH₃ CH₂ SH, (CH₃)₂ SSCH₂ SCH₃, CH₃ SCH₂ CH₂ SCH₃, diisopropyl sulfide, p-dioxane, or tetrahydrofuran. Preferred Lewis bases are (CH₃)₂ S, (CH₃ CH₂)₂ S, CH₃ CH₂ SH, (CH₃ S)₂ CH₂, tetrahydrothiophene or (CH₃)₂ SO. Preferably, the molar ratio of the Lewis base to the initiator should be greater than 6, although ratios as low as 1.1 may be used. The MWD decreases with an increase of [LB]/[Initiator].

The polymers of this invention generally have a narrow molecular weight distribution. The polydispersity is in the range of about 1.0 to about 2.4.

The polymers of this invention are useful for coatings, sealing materials, and adhesives.

In the following embodiments of the invention, temperatures are in degrees Celsius unless otherwise specified. Molecular weights (weight M_(w) and number M_(n) average) were determined by gel permeation chromatography (GPC); polydispersity, D, is given by the ratio of M_(w) /M_(n).

The most preferred embodiments are represented by examples: 1, 3, 4, 17, 23, and 25.

EXAMPLES

The vinyl ethers used were purified by stirring for 48 h with KOH pellets, followed by refuxing over CaH₂, and finally distillation from CaH₂. This procedure was repeated a minimum of three times. Methylene chloride (EM Science, 99.9%) and hexane (Phillips, Spectro Grade) were refluxed over CaH₂ and distilled from CaH₂ ; this procedure was repeated a minumum of three times. Sometimes hexane was purified by distillation from a solution containing living polystyrene. Dioxane (Baker, Baker-Analyzed) was used after drying over molecular sieves. Tetrahydrofuran (EM Science, 99.9%) was used after distillation over sodium-potassium alloy. Methyl sulfide (Aldrich, gold label, anhydrous, 99+%), ethyl sulfide (Aldrich, 98%), n-propyl sulfide (Aldrich, 97%), isopropyl sulfide (Aldrich, 98%), bis(methylthio)methane (Aldrich, 99+%), ethanethiol (Aldrich, 97%), tetrahydrothiophene (Aldrich, 99%) benzaldehyde (Aldrich, 99+%) benzaldehyde dimethyl acetal (Aldrich, 99%), DMSO (Aldrich, gold label, anhydrous, 99+%), fluorosulfonic acid (Columbia, distilled), trifluoromethanesulfonic acid (fluka, purum, >98%), boron trifluoride-methyl sulfide complex (Aldrich), trimethylsilyl triflate (Aldrich, 99%), Magic acid (Aldrich, 25%, 4FSO₃ H.SbF₅), and oleum (Baker, 20%) were used without further purification.

EXAMPLES 1-28 Living Cationic Polymerization of Vinyl Ethers Method A

To a three-necked RB flask, which had been oven-dried, equipped with magnetic stirring, a dropping funnel, and under an argon atmosphere, was added solvent in varying amounts depending on the monomer solution concentration, such that the total solvent volume equaled 120-125 mL. The solvent was then cooled to the indicated temperature, and a solution of an initiator consisting of a proton source (HA), or HA and a Lewis acid, or a carbenium or siliconium ion source, or a carbenium ion source and a Lewis acid, and Lewis base was added, followed by stirring for 10-15 min. All of the monomer was added dropwise to this solution of an initiator and Lewis base. Stirring was continued for 3-15 h when using CH₂ Cl₂ as solvent and for 6-24 h when using hexane as solvent. The living polymerization was quenched by adding a chilled solution of a 10% t-butylamine/methanol solution. The polymer was isolated by stripping solvent (120-125 mL).

Method B

The initiator solution was injected in one portion into the cooled solution of the monomer and Lewis base. The rest of the procedure was the same as Method A.

Results shown in Tables 1 and 2 are for the preferred Lewis bases. Results of polymerizations under inoperative conditions for producing living polymers are shown in Tables 3 and 4.

                                      TABLE 1                                      __________________________________________________________________________     Ex.     Reaction              Lewis                                            No.                                                                               Solvent                                                                             Method                                                                              Temp. Initiator                                                                             Mmol                                                                               Base   Mmol                                      __________________________________________________________________________      1 CH.sub.2 Cl.sub.2                                                                   A    -30° C.                                                                       Me.sub.3 SiT.sub.f.sup.a                                                              0.9 Me.sub.2 S                                                                            30                                         2  "   "    "      "     "    "     "                                          3 Hexane                                                                              "    "      "     "    "     "                                          4 CH.sub.2 Cl.sub.2                                                                   "    "      "     "    "     "                                          5  "   "    "     T.sub.f H                                                                             "    "     7.2                                        6  "   "    "     Me.sub.3 SiT.sub.f                                                                    "   Et.sub.2 S                                                                            15                                         7  "   "    "     T.sub.f H                                                                             "    "     "                                          8  "   "    "      "     "   Me.sub.2 SO                                                                           8.0                                        9  "   "    -60° C.                                                                        "     "    "     7.2                                       10 Hexane                                                                              B    -5 to 0° C.                                                                   EtAlCl.sub.2                                                                          1.0 Me.sub.2 S                                                                            60                                                           H.sub.2 O                                                                             0.83                                                 11 CH.sub.2 Cl.sub.2                                                                   A    -30° C.                                                                       BF.sub.3.Me.sub.2 S                                                                   0.94                                                                                "     26                                                           MeOH   1.0                                                  12  "   "    "     BF.sub.3.Me.sub.2 S                                                                   0.94                                                                                "     "                                                            H.sub.2 O                                                                             0.50                                                 13  "   "    "     BF.sub.3.Me.sub.2 S                                                                   0.94                                                                                "     "                                                            HOAc   1.0                                                  14  "   "    "     BF.sub.3.Me.sub.2 S                                                                   0.94                                                                                "     "                                                            PhCH(OMe).sub.2                                                                       1.0                                                  15  "   "    "     BF.sub.3.Me.sub.2 S                                                                   0.94                                                                               EtSH.sup.b                                                                            4.5                                       16  "   "    -70° C.                                                                       T.sub.f H                                                                             1.8 (CH.sub.3 S).sub.2 CH.sub.2                                                           3.7                                       17  "   B    -30° C.                                                                       BF.sub.3 Et.sub.2 O                                                                   5   Me.sub.2 S                                                                            30                                                           PhC(O)H                                                                               1.0                                                  18  "   "    -30° C.                                                                       T.sub.f H                                                                             1.0 (n-Pr).sub.2 S                                                                        30                                        19  "   "    "      "     1.0 (iso-Pr).sub.2 S                                                                      16.7                                      20  "   "    "     BF.sub.3 OEt.sub.2                                                                    1.0 Dioxane                                                                               15                                                           PhCH(OMe).sub.2                                                                       0.7                                                  21  "   "      0° C.                                                                       BF.sub.3 OEt.sub.2                                                                    1.0  "     "                                                            PhCH(OMe).sub.2                                                                       0.7                                                  22  "   "    -30° C.                                                                       BF.sub.3 OEt.sub.2                                                                    7   THF    42                                                           PhCH(OMe).sub.2                                                                       0.7                                                  23  "   "    "     BF.sub.3 OEt.sub.2                                                                    14  Me.sub.2 S                                                                            42                                                           PhCH(OMe).sub.2                                                                       0.7                                                  24  "   "    "     FSO.sub.3 H                                                                           1.0  "     30                                        25  "   "    "     FSO.sub.3 H.                                                                          1.0  "     26                                                           SbF.sub.5                                                   26  "   "    "     H.sub.2 SO.sub.4                                                                      0.8  "     10                                                           SO.sub.3                                                                              0.2                                                  27  "   "    "     T.sub.f H                                                                             0.68                                                                               Tetrahydro                                                                            17.0                                                                    thiophene                                        28  "   "    "     T.sub.f H                                                                             25  Me.sub.2 S                                                                            133                                       __________________________________________________________________________      .sup.a T.sub.f = CF.sub.3 SO.sub.3                                             .sup.b EtSH serves a dual function as a Lewis base and as a proton source

                  TABLE 2                                                          ______________________________________                                         Ex.  R of               Product                                                No.  RO--CH═CH.sub.2 Mmol                                                                      Yield    -- M.sub.w                                                                           -- M.sub.n                                                                           -- M.sub.w /-- M.sub.n                ______________________________________                                          1   Isobutyl    65     6.76 g 6750  6640  1.02                                 2   "          130     13.43  13800 11700 1.18                                 3   "          260     5.76   10100 9340  1.08                                 4   "          130     13.60  17700 16800 1.05                                 5   "          "       13.29  10100 8290  1.22                                 6   "          "       14.22  14400 11400 1.26                                 7   "          "       13.56  13600 11100 1.24                                 8   "          "       14.30  7420  4650  1.60                                 9   Ethyl      "       10.1   5090  3100  1.64                                10   Isobutyl    65     5.83   15600 12900 1.21                                11   "          "       6.89   2830  1350  2.10                                12   "          "       6.19   9340  7690  1.21                                13   "          "       6.18   3390  2820  1.20                                14   "          "       6.78   6190  4820  1.28                                15   "          "       6.67   3270  2250  1.45                                16   Ethyl      260     19.67  27700 19200 1.44                                17   Isobutyl    61     6.82   13700 13400 1.02                                18   "           65     6.72   12400 7860  1.58                                19   "          "       6.66   14100 7260  1.95                                20   "           61     6.41   21200 9100  2.34                                21   "          "       6.31   23000 9740  2.37                                22   "          "       6.18   19900 9810  2.03                                23   "          "       6.84   9120  9280  0.98                                24   "          "       6.38   6440  3790  1.70                                25   "          "       6.58   3860  3670  1.05                                26   "          "       5.98   717   408   1.75                                27   "          "       6.26   8180  7470  1.10                                28   Methyl     550     30.8   1190  1030  1.16                                ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     Exper-                                                                         iment    Reaction          Lewis                                               No. Solvent                                                                             Method                                                                              Temp.                                                                              Initiator                                                                           Mmol                                                                               Base    Mmol                                        __________________________________________________________________________     1   CH.sub.2 Cl.sub.2                                                                   A    -30 T.sub.f H                                                                           0.9 p-Dithiane                                                                             2.7                                         2   "    "    "    "   "   (i-Pr).sub.2 S                                                                         7.2                                         3   "    "      0  "   "   Pyridine Oxide                                                                         1.0                                         4   "    "    -30 T.sub.f H                                                                           "   Ph.sub.2 SO                                                                            3.6                                         5   "    "    "    "   "   CH.sub.3 CO.sub.2 Et                                                                   15.0                                        6   "    "    "    "   "   CH.sub.3 CN                                                                            "                                           7   "    "    "    "   "   PhCO.sub.2 Et                                                                          "                                           8   "    "    "   Me.sub.3 SiT.sub.f                                                                   1.80                                                                              p-Dioxane                                                                              60                                          9   "    "    "    "   "   CH.sub.3 I                                                                             15.0                                        10  "    "    "    "   "   Me.sub.3 CI                                                                            "                                           __________________________________________________________________________

                  TABLE 4                                                          ______________________________________                                         Experi-                                                                        ment  R of               Product                                               No.   RO--CH═CH.sub.2 Mmol                                                                      Yield    -- M.sub.w                                                                           -- M.sub.m                                                                          -- M.sub.w /-- M.sub.n                ______________________________________                                         1     i-Bu       130     13.45  35100 1930 18.2                                2     "          "       13.18  27900 3520 7.94                                3     "          "       13.46  18200 2590 7.00                                4     "          "       13.32  12700 745  17.1                                5     "          "       13.94  18900 2560 7.40                                6     "          "       13.02  17400 2430 7.16                                7     "          "       14.37  20100 2470 8.16                                8     "          "       13.54  34300 5150 6.66                                9     "           65     7.33   32100 3390 9.47                                10    "          "       7.19   33100 5840 5.67                                ______________________________________                                    

EXAMPLE 29 Effect of [LB]/[Initiator] on MWD

The MWD was found to be dependent on the [LB]/[Initiator] ratio. Results of experiments for the polymerization of isobutyl vinyl ether in the presence of (CH₃)₂ S that demonstrated this are shown in Table 5. Experiments A-G were run under the following conditions: I=T_(f) H (0.90 mmol), solvent=CH₂ Cl₂, reaction temperature=-30° C., yields yields-quantitative. Experiments H-O were run under the following conditions: I=Me₃ SiT_(f) (0.90 mmol), solvent=CH₂ Cl₂, reaction temperature=-30° C., yields-quantitative.

                  TABLE 5                                                          ______________________________________                                         -- M.sub.w /-- M.sub.n Dependence on [LB]/[I]                                  Experiment      [LB]/[I] -- M.sub.w /-- M.sub.n                                ______________________________________                                         A               2        1.74                                                  B               "        1.79                                                  C               4        1.58                                                  D               8        1.32                                                  E               "        1.34                                                  F               16.7     1.23                                                  G               "        1.21                                                  H               0        5.62                                                  I               "        7.71                                                  J               4        1.56                                                  K               "        1.68                                                  L               16.7     1.38                                                  M               "        1.33                                                  N               33.3     1.18                                                  O               "        1.20                                                  ______________________________________                                    

EXAMPLE 30 M_(n) Dependence on [M]_(o) /[I]_(o)

Isobutyl vinyl ether was polymerized by Me₃ SiT_(f) (0.90 mmol) in the presence of Me₂ S (30 mmol) using CH₂ Cl₂ as solvent at a reaction temperature of -30° C. using Experimental Method B described above. Quantitative yields of polymers were obtained. The results of these experiments are shown in Table 6, A-H. A similar series was done with triflic acid initiator; the results of these experiments are shown in Table 6, I-N.

                  TABLE 6                                                          ______________________________________                                         Dependence of M.sub.n on [M].sub.o /[I].sub.o                                  Experiment                                                                               [M].sub.o /[I].sub.o                                                                    -- M.sub.n (calc).sup.1                                                                    -- M.sub.n                                                                           -- M.sub.w /-- M.sub.n                    ______________________________________                                         A         36.1     3615        7440  1.03                                      B         "        "           9390  1.06                                      C         72.2     7231        13600 1.09                                      D         "        "           17900 1.11                                      E         108.3    10846       23100 1.14                                      F         "        "           32600 1.09                                      G         144.4    14462       46600 1.15                                      H         "        "           43800 1.15                                      I         32.5     3255        1740  1.08                                      J         "        "           1950  1.07                                      K         65       6510        4160  1.04                                      L         "        "           4300  1.0                                       M         97.5     9765        6520  1.04                                      N         "        "           6130  1.12                                      ______________________________________                                          .sup.1 --M.sub.n (calc) = [M].sub.o M.sub.1                                    Reaction time: .sup.a 1 h, .sup.b 2 h, .sup.c 3 h.                       

COMPARATIVE EXPERIMENT Effect of H₂ O on the Polymerization System

The addition of H₂ O to the isobutyl vinyl ether/Me₃ SiT_(f) /Me₂ S/CH₂ Cl₂ polymerization system resulted in a decrease of M_(w) and an increase of M_(w) /M_(n). Water was completely consumed in a very efficient chain transfer to monomer reaction as can be seen from the fact that M_(n) =M_(n) (calc)=M_(o) /([Me₃ SiT_(f) ]_(o) +[H₂ O]). l

The effect of ethanol is similar. These results indicate that polyalkyl vinyl ethers having controlled M_(w) and M_(w) /M_(n) in the range of 1.1-1.5, can be obtained by controlling the [Me₃ SiT_(f) ]/[H₂ O] ratio.

                  TABLE 7                                                          ______________________________________                                         Effect of Added Water                                                          Exper-                                                                               [H.sub.2 O]                                                                            [Me.sub.3 SiT.sub.f ] +                                                                    -- M.sub.n       10.sup.4                            iment (mmol)  [H.sub.2 O] (mmol)                                                                         (calc)                                                                               -- M.sub.n                                                                          -- M.sub.w /-- M.sub.n                                                               (1/-- M.sub.n)                      ______________________________________                                         A     --      0.9         7234  7510 1.04  1.33                                B     --      "           "     9370 1.03  1.07                                C     0.9     1.8         3617  3590 1.27  2.79                                D     "       "           "     3810 1.25  2.62                                E     1.8     2.7         2422  2340 1.42  4.27                                F     "       "           "     1810 1.90  5.52                                G     3.6     4.5         1607  1360 2.86  7.35                                H     "       "           "     1060 2.86  9.43                                ______________________________________                                    

Although preferred embodiments of the invention have been illustrated and described hereinabove, it is to be understood that there is no intent to limit the invention to the precise constructions herein described. Rather, it is to be further understood that the right is reserved to all changes and modifications coming within the scope of the invention as defined by the appended claims. 

What is claimed is:
 1. A process for the living cationic polymerization of vinylic unsaturated monomers containing electronic donating substituents, comprising contacting said vinylic unsaturated monomers under polymerizing conditions at a temperature of about -80° C. to about 0° C. in a suitable solvent, in the presence of an initiating combination consisting essentially of a Lewis base selected from the group consisting of CH₃ SR¹, wherein: R¹ is straight chain C₁ to alkyl; (CH₃ CH₂)₂ S; (CH₃ CH₂ CH₂)₂ S; (CH₃)₂ SSCH₂ SCH₃ ; CH₃ CH₂ SH; (CH₃)₂ SO; CH₃ SCH₂ SCH₃ ; CH₃ SCH₂ CH₂ SCH₃ ; tetrahydrothiophene: tetrahydrofuran: diisopropyl sulfide: and p-dioxane, and a second component selected from: a proton source; a proton source and a Lewis acid; a carbenium or siliconium ion source; and a carbenium or siliconium ion source and a Lewis acid; provided that when the Lewis base is dioxane, the Lewis acid RAICL₂, where R is C₁ to C₄ alkyl, is not present.
 2. The process of claim 1 wherein the initiating combination is a proton source and a Lewis base.
 3. The process of claim 1 wherein the initiating combination is a proton source, Lewis acid and a Lewis base.
 4. The process of claim 1 wherein the initiating combination is a carbenium ion or siliconium ion source and a Lewis base.
 5. The process of claim 4 wherein the initiating combination is a siliconium ion source and a Lewis base.
 6. The process of claim 4 wherein the initiating combination is a carbenium ion source and a Lewis base.
 7. The process of claim 1 wherein the initiating combination is a carbenium or siliconium ion source, a Lewis acid and a Lewis base.
 8. The process of claim 1 or 2 or 3 or 4 or 5 or 6 or 7 wherein the product is a living polymer.
 9. The process of claim 8 where the vinylic unsaturated monomers are selected from the group of monomers consisting of styrenes with para alkyl or alkoxy groups containing C₁ to C₆ carbon atoms, alkyl vinyl ethers or aralkyl vinyl ethers, where the alkyl groups can contain one to twenty carbon atoms, and optionally halogen atoms or ether linkages, and N-vinyl carbazole.
 10. The process of claim 8 wherein the monomer used is selected from the group consisting of methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether.
 11. The process of claim 9 or claim 10 wherein the solvent is selected from the group comprising dichloromethane or hexane.
 12. The process of claim 11 carried on in an inert gas atmosphere.
 13. The process of claim 12 carried on in a water free atmosphere.
 14. The process of claim 12 carried out in the presence of water.
 15. The process of claim 13 or claim 14 conducted at atmospheric pressure.
 16. The process of claim 15 wherein the molar ratio of the Lewis base to the initiator is in excess of 6 to
 1. 17. The process of claim 2 wherein the proton source is selected from the group consisting of CF₃ SO₃ H, H₂ SO₄, FSO₃ H, and HClO₄.
 18. The process of claim 3 wherein the proton source is selected from the group consisting of HCO₂ R (where R is C₁ -C₄ alkyl), HOR, HSR and H₂ O and the Lewis acid is selected from the group consisting of BF₃, RAlCl₂, PF₅ and SbF₅.
 19. The process of claim 17 or claim 18 wherein the Lewis Base is selected from the group consisting of CH₃ SR¹, wherein: R¹ is straight chain C₁ to C₄ alkyl; (CH₃ CH₂)₂ S; (CH₃ CH₂ CH₂)₂ S; (CH₃)₂ SSCH₂ SCH₃ ; CH₃ CH₂ SH; (CH₃)₂ SO; CH₃ SCH₂ SCH₃ : CH₃ SCH₂ CH₂ SCH₃ ; tetrahydrothiophene; tetrahydrofuran; diisopropyl sulfide; and p-dioxane.
 20. The process of claim 4 wherein the carbenium and siliconium ion sources are selected from the group consisting of CF₃ SO₃ R, CF₃ SO₃ SiR₃, R² CH(OR)₂, R² C(OR)₃ and R² C(O)H, where R² is phenyl or C₁ -C₆ alkyl, and R is as defined in claim
 18. 